The goal of increasing the specific capacity of anodes of lithium-ion batteries (LIBs) by nearly a factor of 10 through the substitution of graphite has tremendously influenced the direction of recent scientific efforts. Graphite has a theoretical capacity of about 372 mAh/g compared to silicon (Si) having a theoretical capacity of only about 3572 mAh/g. Utilization of Si promotes a high capacity lithium (Li) alloying reaction which produces a Li-rich phase (Li15Si4) compared with an intercalation reaction with graphite (LiC6). However, the increased accommodation of Li+ ions during charge-discharge cycles induces large volume variations (as much as about 370%) and stress on a bulk anode matrix that may ultimately shorten the useful life of the anode. In view of this hindrance, different strategic schemes have been pursued to alleviate the effect of volume expansion including the use of amorphous thin films, nanowires, nanotubes, and porous morphologies. Despite these advances, a significant capacity degradation during charge-discharge cycles (in the following called “cycling”) is still observed, suggesting electrode fracturing and eventual electrical contact losses.